Development of a Large‐Scale Stopped‐Flow System for Heterogeneous Olefin Polymerization Kinetics

Taniike, Toshiaki; Sano, Shinya; Ikeya, Mitsuhiro; Thang, Vu Quoc; Terano, Minoru

doi:10.1002/mren.201200003

Cited by 18 publications

(10 citation statements)

References 19 publications

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“…4). Stopped-flow-type polymerization was selected, as short-time polymerization can minimize the transient nature of active sites 25), 26) . The polymerization was performed for 0.4 s at 303 K under 1 atm of propylene using dry n-heptane as a solvent and tri-i-butyl aluminum (TiBA) as an activator.…”

Section: Methodsmentioning

confidence: 99%

High-precision Molecular Modelling for Ziegler-Natta Catalysts

Taniike

Terano

2018

J. Jpn. Petrol. Inst.

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A major bottleneck of computational chemistry in heterogeneous catalysis is found at the difficulty and resultant inaccuracy of molecular models for catalyst surfaces. Here, we review our recent efforts to establish a highprecision molecular model of heterogeneous Ziegler-Natta catalysts for olefin polymerization, which was mainly based on the validation of potential molecular models for a set of experimentally known facts in density functional calculations. The coadsorption of donor molecules with Ti mononuclear species on MgCl2 surfaces is proposed as an experimentally consistent molecular model, and its successful utilization in a structure-performance relationship study for donors is described.

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Section: Methodsmentioning

confidence: 99%

High-precision Molecular Modelling for Ziegler-Natta Catalysts

Taniike

Terano

2018

J. Jpn. Petrol. Inst.

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“…In order improve the flow stability and the volume scalability, the LSF technique was developed [21]. The LSF apparatus is illustrated in Figure 3.…”

Section: Development Of Large-scale Stopped-flow Techniquementioning

confidence: 99%

“…Scalability test in LSF propylene polymerization. The tube length was fixed at 0.15 s, while the cumulated flow volume was increased [21]. …”

Section: Figures Scheme and Tablesmentioning

confidence: 99%

“…Moreover, when the polymerization is performed beyond 1.0 s, the technique suffers from inefficient flow of reaction slurry that is caused by a larger amount of polymer formation inside the Teflon tube. In order to alleviate these problems, Taniike et al developed a large-scale stopped-flow (LSF) system based on the identical principle of the conventional SF technique but with a greatly differed system design [21]. The new system offers improved flow stability for sufficiently elongated polymerization (up to several seconds) and the volume scalability to increase the polymer yield per batch.…”

Section: Introductionmentioning

confidence: 99%

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Development of Large-Scale Stopped-Flow Technique and its Application in Elucidation of Initial Ziegler–Natta Olefin Polymerization Kinetics

et al. 2019

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The stopped-flow (SF) technique has been extensively applied to study Ziegler–Natta (ZN) olefin polymerization kinetics within an extremely short period (typically <0.2 s) for understanding the nature of the active sites as well as the polymerization mechanisms through microstructure analyses of obtained polymers. In spite of its great applicability, a small amount of polymer that is yielded in a short-time polymerization has been a major bottleneck for polymer characterizations. In order to overcome this limitation, a large-scale SF (LSF) system has been developed, which offers stable and scalable polymerization over an expanded time range from a few tens milliseconds to several seconds. The scalability of the LSF technique has been further improved by introducing a new quenching protocol. With these advantages, the LSF technique has been effectively applied to address several unknown issues in ZN catalysis, such as the role of physical and chemical transformations of a catalyst on the initial polymerization kinetics, and regiochemistry of ZN propylene polymerization. Here, we review the development of the LSF technique and recent efforts for understanding heterogeneous ZN olefin polymerization catalysis with this new system.

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“…On the other hand, some catalysts show induction periods that can be quite long (several seconds), making them difficult to study with standard stopped flow equipment. Stopped flow reactors similar to the ones developed here, but with much larger reservoirs (1 or 2 litres instead of 500 ml each) might be one solution to overcoming this problem …”

Section: Introductionmentioning

confidence: 99%

Specialised tools for a better comprehension of olefin polymerisation reactors

McKenna

Boisson

Monteil

et al. 2013

Macromolecular Symposia

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Summary 2 laboratory‐scale reactor systems suitable for gas phase, and for solution or slurry polymerisations are discussed. The underlying concept behind the design and use of these reactors is that they can be used to understand the impact of conditions specific to different time scales and/or length scales inherent to large reactors that are difficult to recreate at the laboratory scale. For instance the fixed bed gas phase reactor is used to study the influence of different relative gas/solid velocities on the evolution of the molecular weight distribution of the nascent polymer. It is shown that in certain conditions, changing the heat transfer characteristics does not change the observed yield, but will impact the polymer properties. In the case of the solution reactor, the concept is to design and use a reactor to study the activation of unsupported metallocenes. Here it is shown that different metallocenes have very different activation profiles to a point where a stopped flow reactor might not be the ideal tool for their study.

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Development of a Large‐Scale Stopped‐Flow System for Heterogeneous Olefin Polymerization Kinetics

Cited by 18 publications

References 19 publications

High-precision Molecular Modelling for Ziegler-Natta Catalysts

High-precision Molecular Modelling for Ziegler-Natta Catalysts

Development of Large-Scale Stopped-Flow Technique and its Application in Elucidation of Initial Ziegler–Natta Olefin Polymerization Kinetics

Specialised tools for a better comprehension of olefin polymerisation reactors

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